CN109233338A - A kind of disperse dye compound and its synthetic method and purposes - Google Patents

A kind of disperse dye compound and its synthetic method and purposes Download PDF

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Publication number
CN109233338A
CN109233338A CN201810947117.9A CN201810947117A CN109233338A CN 109233338 A CN109233338 A CN 109233338A CN 201810947117 A CN201810947117 A CN 201810947117A CN 109233338 A CN109233338 A CN 109233338A
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reaction
ugi
dye compound
disperse dye
dyestuff
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CN109233338B (en
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冯高峰
钱红飞
李欢欢
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University of Shaoxing
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University of Shaoxing
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs

Abstract

A kind of disperse dye compound of the present invention and its synthetic method and purposes, it is characterized in that, the following steps are included: (1) Ugi reacts: in organic solvent, aldehyde, aniline, formic acid and cyclohexyl isonitrile being carried out tetra- component reaction of Ugi, reaction solution obtains Ugi product through filtering, organic solvent washing；(2) hydrolysis: in alcohols solvent, Ugi product is added and acid carries out selective hydrolysis, reaction solution is neutralized, organic solvent is extracted, is concentrated under reduced pressure, is dried to obtain hydrolysate, that is, synthesizes the coupling component of azo dispersion dyes；(3) coupling reaction: in the presence of organic acid, the in the mixed solvent of alcohols and water, by gained coupling component and 2, the chloro- 4- nitrophenyl diazonium salt of 6- bis-, which is coupled, adjusts reacting liquid pH value, solid is filtered, washed, is dried etc. obtains Novel disperse dyestuff compound.The disperse dye compound that the present invention synthesizes has significant effect to the dyeing of polyester fiber, Fypro.

Description

A kind of disperse dye compound and its synthetic method and purposes
Technical field:
The present invention relates to a kind of disperse dye compound and its synthetic methods and purposes.
Background technique:
Disperse dyes are applied to the dyeing of acetate fiber earliest, after with synthetic fibers development, especially polyester fiber The development of (terylene) and develop rapidly.Disperse dyes are various in style, chromatography is complete, are widely used, and become dyestuff row Most important major class branch in the industry.China is the first big producer of disperse dyes in the world, is had in the international market relatively strong The market competitiveness.Disperse dyes structure is simple, and molecular weight is lower, is free of water soluble group, though contain polar group in molecule (such as hydroxyl, amino, hydroxyl alkylamino, cyanogen alkylamino), still belongs to nonionic dye, it is also current hydrophobic fibre (as gathered Ester, polyamide etc.) dyeing a class of dyes the most main.There are two types of mode classifications for disperse dyes, first is that according to application performance, it can Disperse dyes are divided into low form, high temperature modification and middle warm type three categories；Second is that according to chemical structure, it can be by disperse dyes point For azo, Anthraquinones and heterocyclic and a small amount of quinophthalone class, methine class, ortho-nitrophenyl amine etc..Wherein azo-type The disperse dyes of structure are most important one kind, account about 60%.The disperse dyes of azo-type structure have than more complete color Spectrum can obtain different colours, different dyeabilities by changing the electronic effect of substituent group on diazo component and coupling component Dyestuff.Dyestuff can be made to generate hyperchromic effect as diazo component introduces electron-withdrawing group or coupling component introducing electron-donating group；With Its vividness and absorption intensity can be improved in heterocycle substitution phenyl ring.In recent years, since heterocycle type disperse dye bright in color light, color development are strong Degree is high, fastness ability is good, has preferable hyperchromic effect and higher molar extinction coefficient, and have good dyeability, makes It becomes dyestuff circle and studies a more field.
Currently, as hyperfine polyester fiber, environment-friendly type acid fiber by polylactic, differential terylene easily contaminate fiber and tencel Occur, the dyeing ability of most of existing disperse dyes has shown deficiency.Disperse dyes show as Yi Jinyi on fiber and go out The phenomenon that, lead to that its washing fastness is poor, application performance is bad.To find out its cause, mainly disperse dyes and these fibers is affine Power is poor, and when the temperature is excessively high, dye molecule warm-up movement aggravation is migrated from fibrous inside to fiber sheath.Disperse dyes heat is moved Fastness decline problem caused by moving is by the common concern of insider institute, research day of the domestic and international people in the industry to this respect Become to increasing.
The main method for improving affinity between disperse dyes and fiber is the molecular weight for effectively improving disperse dyes, with The increase of molecular weight, the Van der Waals force enhancing between dye molecule and fiber, resistance to thermal migration, the dyeabilities such as fastness to sublimation It can be improved.Therefore, increase disperse dyes to the affinity of fiber, be expected to fundamentally solve and improve the above problem.It opens Disperse dyes that send out structure novel, that dyeability is excellent have significant application value.
Summary of the invention:
The first aspect of the present invention purpose is to provide a kind of disperse dye compound, and the disperse dye compound is to polyester fibre The dyeing of dimension, Fypro has significant effect.
The technical solution adopted by the present invention is as follows:
A kind of disperse dye compound, structural formula are as shown in Equation 1:
In formula: R1For H, CH3, R2For H, Br.
A kind of disperse dye compound of the present invention, is structurally characterized in that: molecular weight and molecular volume are moderate, contain One amide groups structural unit (- CONH-).Those design features have important shadow to the raising of the dyeability of the new dye It rings:
(1) dye molecule volume and molecular weight effectively increase, and improve the contact surface between dyestuff and fiber, enhance The Van der Waals force of dyestuff and fiber improves its dyeability and color fastness to improve the affinity of dyestuff and fiber.
(2) by introduce amide groups (- CONH-) this characteristic group, can in fiber by hydrogen group, for hydrogen group shape It at hydrogen bond, and is mutually suitable for enhancing mutual active force with the structure of polyester fiber, to improve dyeability.
(3) in azo dyes synthesis, the group on diazo component has weight to the maximum absorption wavelength and color of dyestuff It influences.In the identical situation of coupling component, select different substituent groups that can obtain the idol of different colours in diazo component Nitrogen dyestuff provides great convenience for the diversity synthesis of azo dispersion dyes.
A kind of disperse dye compound of the invention can be selected from one kind of following compound:
The second aspect of the present invention purpose is to provide a kind of preparation method of aforementioned disperse dye compound, and feature exists In, comprising the following steps:
(1) Ugi reacts: in organic solvent, by a certain amount of aldehyde, aniline, formic acid and cyclohexyl isonitrile in certain temperature Lower progress tetra- component reaction of Ugi, reaction solution obtain Ugi product through filtering, organic solvent washing；
(2) hydrolysis: in alcohols solvent, Ugi product is added and certain density acid is selected at a certain temperature Property hydrolysis, reaction solution is neutralized, organic solvent extract, is concentrated under reduced pressure, is dried to obtain hydrolysate, that is, synthesize azo dispersion dyes Coupling component；
(3) coupling reaction: in the presence of organic acid, the in the mixed solvent of alcohols and water, by gained coupling component and 2,6- bis- Chloro-4 nitrophenyl diazonium salt is coupled at a certain temperature, adjusts reacting liquid pH value, solid is filtered, washed, is dried Obtain Novel disperse dyestuff compound.
Reaction equation of the present invention is as follows:
In equation, R is 4-Me and 2-Br
Further it is provided in:
In step (1):
The organic solvent is any one in toluene, methanol, ethyl alcohol or acetonitrile.
The molar ratio of the aldehyde, aniline, cyclohexyl isonitrile, formic acid are as follows: 1:1~1.2:1~1.2:1~1.2.
The reaction temperature is 40-100 DEG C, and reaction condition is more mild, the reaction time are as follows: 36-48h.
In step (2):
Shown in alcohols solvent are as follows: methanol, ethyl alcohol, any one in isopropanol.The acid are as follows: hydrochloric acid, sulfuric acid, phosphorus Any one in acid.
The mass concentration of the acid are as follows: 36.5% (hydrochloric acid), 40%-60% (sulfuric acid).
The molar ratio of the Ugi product and acid are as follows: 1:10-20.
The reaction temperature is 60-120 DEG C, the reaction time are as follows: 2-6h.
The alkali are as follows: sodium hydroxide, potassium hydroxide, any one in sodium bicarbonate, molar concentration 2-8mol/L.
The organic solvent that the extraction uses is ethyl acetate or methylene chloride, after organic phase saturated common salt water washing It is dried with anhydrous sodium sulfate.
In step (3):
The organic acid are as follows: formic acid, acetic acid, sulfonic acid, any one in benzoic acid.
The molar ratio of the coupling component and the chloro- 4- nitrophenyl diazonium salt of 2,6- bis- are as follows: 1:1-2.
The reaction temperature is 0-5 DEG C, reaction time 24-36h.
The present invention has significant technical effect due to using above technical scheme.By changing taking for starting material Can be obtained the coupling component of different molecular weight and different molecular volume for base or structure, realize Novel disperse dyestuff molecular volume and Effective control of molecular weight, thus controllable disperse dyeing performance and color fastness.
It is fine in polyester fiber and polyamide that the third aspect of the present invention purpose is to provide a kind of aforementioned disperse dye compound Purposes in dimension dyeing, is verified by experiments, using above-mentioned disperse dye compound, contaminates polyester fiber, Fypro Color, and color fastness test is carried out to 1:1 standard dyeing sample, test result shows the washing of polyester and Fypro dyeing sample Fastness is more significantly improved, and especially fastness to dryheat is significantly improved.
The present invention is elaborated further below in conjunction with the drawings and specific embodiments:
Detailed description of the invention:
Fig. 1 is the hydrogen nuclear magnetic resonance figure of dyestuff 2a of the present invention；
Fig. 2 is the hydrogen nuclear magnetic resonance figure of dyestuff 2b of the present invention；
Fig. 3 is the absorption spectrum curve comparison diagram of dyestuff 2a of the present invention and disperse orange 3.
Fig. 4 is the absorption spectrum curve comparison diagram of dyestuff 2b of the present invention and disperse orange 3.
Specific embodiment:
Embodiment 1: dyestuff 2a
Embodiment 1-1: the preparation of dyestuff 2a
(1) tetra- component reaction of Ugi:
In 250mL round-bottomed flask, sequentially add anhydrous methanol (150mL), aniline (4.39mL, 48.16mmol, 1.05eq), p-tolyl aldehyde (4.9mL, 48.16mmol, 1.05eq), formic acid (2.07mL, 55.04mmol, 1.2eq), and Cyclohexyl acetonitrile (5.69mL, 45.87mmol, 1.0eq).Reaction mixture heating stirring 48h in 80 DEG C of oil baths, through TLC points Analysis, fully reacting.After reaction solution is cooled to room temperature, at a refrigerator lower layer cooling night, white solid is generated.It filters (when suction filtration Rinsed with the solution of EA:PE=1:5) obtained solid 7.0925g, filtrate is spin-dried for, weigh to obtain 4.6563g.That is gained Ugi product Total 11.7488g, yield add up to 73%.Reaction equation is as follows:
Product confirmation:
IR(film)3273,3085,2926,1668,165,1559,700cm-1.
1H NMR(400MHz,CDCl3)δ8.39(s,1H),7.26-7.25,7.26-7.25(m,3H),7.19-7.16(m, 2H), 7.12 (d, J=8.0Hz, 2H), 7.06 (d, J=8.0Hz, 2H), 5.96 (s, 1H), 5.77 (br d, J=8.0Hz, 1H),3.88-3.81(m,1H),2.30(s,1H),1.95-1.89(m,2H),1.70-1.57(m,3H),1.39-1.30(m, 2H),1.17-1.05(m,3H).
13C NMR(100MHz,CDCl3)δ168.0,163.1,139.4,138.4,131.1,129.6(×2),129.3 (×2),128.9(×2),128.2(×2),127.7,63.6,48.8,32.8,25.5,24.8,24.7,21.1.MS(+ ESI): m/z (%)=351 (52) [M+H+].
(2) hydrolysis:
In 250mL round-bottomed flask, Ugi reaction product (7.0925g, 20.26mmol), anhydrous methanol are sequentially added (70mL), by 17.5mL H2The dense H of O and 17.5mL2SO4(98%) it is added dropwise in flask after mixing.It is heated in 90 DEG C of oil baths 2h is reacted, contact plate is analyzed through TLC, fully reacting.Reaction solution in flask is adjusted to the laggard of pH=7 with 5mol/L NaOH Row extraction, is added water and ethyl acetate washs 2 times, and stratification, organic phase is dried, filtered with anhydrous sodium sulfate, is rotated, dry Weigh to obtain m=6.0156g, yield 92%.Reaction equation is as follows:
Product confirmation:
IR(film)3300,2930,2854,1647,1504,749cm-1.
1H NMR(400MHz,CDCl3) δ 7.33 (d, J=8.4Hz, 2H), 7.23-7.19 (m, 4H), 6.82 (dd, J= 7.6,7.2Hz, 1H), 6.68 (br d, J=8.0Hz, 1H), 6.65 (dd, J=8.8,1.2Hz, 2H), 4.69 (s, 1H), 3.85-3.80 (m, 1H), 2.37 (s, 3H), 1.93-1.81 (m, 2H), 1.72-1.58 (m, 3H), 1.40-1.29 (m, 2H), 1.22-1.03(m,3H).
13C NMR(100MHz,CDCl3)δ170.2,146.8,138.3,136.0,129.9(×2),129.3(×2), 127.3(×2),119.1,113.9(×2),64.1,48.1,33.0,32.8,25.4,24.8,24.7,21.2.MS(+ESI): M/z (%)=323 (100) [M+H+].
(3) disperse dyes synthesize:
1, diazonium salt synthesize: in 50mL round-bottomed flask be added 2,6- Dichloro-4-nitroaniline (0.588g, 2.325mmol, 1.5eq), by 4mL H2It is added drop-wise in flask after the dense HCl of O and 4mL (36.5%) mixing, in 40~60 DEG C of conditions It is lower to be dissolved (about 2h).After solution is cooled to room temperature, it is placed in ice-water bath.By sodium nitrite (0.16g, 2.325mmol, 1.5eq) use 4mL H2O is dissolved in test tube, is placed in ice-water bath and is placed 2min or so.By above-mentioned NaNO2Aqueous solution is slow dropwise It is added, reacts 2h in ice-water bath after being added dropwise to complete.
2, coupling reaction: in 100mL round-bottomed flask, being added 10mL methanol, 2mL acetic acid and 5mL water, in embodiment 1-1 (2) gained coupling component (0.5g, 1.55mmol, 1.0ep), stirring to coupling component are completely dissolved.It, will under the conditions of ice-water bath The chloro- 4- nitrophenyl diazonium salt of 2,6- bis- prepared slowly instills dropwise, stirs at 0~5 DEG C for 24 hours, thin-layer sample application tracking Reaction process adjusts pH to alkalescent, filtering, organic solvent (EA:PE=1:5) with the sodium hydroxide of 5mol/L after completion of the reaction Washing obtains sterling dyestuff 2a, the dry 0.7034g that weighs to obtain, yield 84% using re-crystallizing in ethyl acetate method.Reactional equation Formula is as follows:
The IR of disperse dyes 2a,1H-NMR、13C-NMR and MS data are as follows:
IR(film)2984,1739,1373,1238,1046cm-1.
1H NMR(400MHz,CDCl3) δ 8.26 (s, 2H), 7.83 (d, J=8.8Hz, 2H), 7.35 (d, J=8.0Hz, 2H), 7.22 (d, J=8.0Hz, 2H), 6.67 (d, J=8.8Hz, 2H), 5.92 (d, J=8.0Hz, 1H), 4.88 (s, 1H), 3.84-3.74 (m, 1H), 2.37 (s, 3H), 1.94 (d, J=9.2Hz, 1H), 1.77-1.68 (m, 2H), 1.60 (d, J= 10.0Hz,2H),1.40–1.25(m,2H),1.18-1.12(m,2),1.02–0.99(m,1H).
13C NMR(100MHz,CDCl3)δ169.0,153.8,151.1,145.3,144.9,138.8,135.2,130.2 (×2),127.9(×2),127.0(×2),126.2(×2),124.2(×2),113.3,(×2)61.7,48.8,32.9, 32.6,25.3,24.7,24.6,21.2.
(%)=392 (100) MS (+ESI): m/z, 540 (52) [M+H+].
Embodiment 1-2:
Spectral absorption performance: weighing 0.05 gram of dyestuff 2a, dissolves constant volume in 50mL n,N-Dimethylformamide, dilution Certain multiple makes concentration 0.006g/L, is measured and is inhaled using UV-2450 ultraviolet-uisible spectrophotometer (Japanese Shimadzu Corporation) The curve of spectrum is received, and compared with 3 solution absorption spectra curve of same concentrations 0.006g/L disperse orange.See Fig. 3.
From the absorption spectrum curve in figure it can be found that compared with disperse orange 3, the maximum absorption wavelength of dyestuff 2a is to short Wave direction offsets by 47nm, becomes 420nm from original 467nm.After measured, specific performance index is as shown in following table 1-1:
Table 1-1, dyestuff absorption spectrum performance parameter
。
Embodiment 1-3:
Product fastness properties detection: the dyeing by dyestuff 2a manufactured in the present embodiment and disperse orange 3, applied to terylene. Its test method is as follows, and dyeability result is as shown in table 1-2.
Test method: 0.5000g dyestuff 2a (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's Mother liquor draws this mother liquor into the dye liquor of various concentration, 180min is dyed under the conditions of 130 DEG C, obtains 1:1 standard color sample The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO105-P01:1993 (E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
Table 1-2, dyestuff compare the fastness properties of dyeing terylene
In terms of upper table experimental data: every fastness properties of dyestuff 2a and disperse orange 3 only have improvement slightly, still, Fastness to dryheat has achieved the effect that expected imagination, and staining fastness increase rate is larger, illustrates that dyestuff 2a really has fiber Biggish affinity, dyestuff are not easy to come out from internal migration.
Embodiment 1-4:
Dyeing by dyestuff 2a manufactured in the present embodiment and disperse orange 3, applied to Fypro.Its test method is such as Under, dyeability result is as shown in table 1-3.
Test method: 0.5000g dyestuff 2a (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's Mother liquor draws this mother liquor into the dye liquor of various concentration, 60min is dyed under the conditions of 100 DEG C, obtains 1:1 standard color sample The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO105-P01:1993 (E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
The fastness properties that table 1-3, dyestuff dye Fypro compare
In terms of upper table experimental data: dyestuff 2a has greatly improved than every fastness properties of disperse orange 3, to various fibres The staining fastness increase rate of dimension is larger, and especially fastness to dryheat has achieved the effect that expected imagination, illustrates that dyestuff 2a is certain There is biggish affinity to fiber, dyestuff is not easy to come out from internal migration.
Embodiment 2: dyestuff 2b
Embodiment 2-1: the preparation of dyestuff 2b
(1) tetra- component reaction of Ugi:
In 250mL round-bottomed flask, sequentially add anhydrous methanol (150mL), aniline (4.39mL, 48.16mmol, 1.05eq), o-bromobenzaldehye (5.63mL, 48.16mmol, 1.05eq), formic acid (2.07mL, 55.04mmol, 1.2eq), hexamethylene Base acetonitrile (5.69mL, 45.87mmol, 1.0eq).Reaction mixture heats 48h in 80 DEG C of oil baths, analyzes, has reacted through TLC Entirely.After reaction solution is cooled to room temperature, at a refrigerator lower layer cooling night, white solid is generated.Suction filtration (uses EA:PE=when suction filtration The solution of 1:5 rinses) obtained solid 7.8915g, filtrate is spin-dried for, weigh to obtain 6.7571g.Gained Ugi product is total 14.6486 yield adds up to 77%.Reaction equation is as follows:
Product confirmation:
IR(film)3347,2929,1692,1663,766,700cm-1.
1H NMR(400MHz,CDCl3) δ 8.42 (s, 1H), 7.50 (d, J=6.8Hz, 1H), 7.31-7.29 (m, 3H), 7.19-7.18 (m, 3H), 7.12-7.06 (m, 2H), 6.32 (s, 1H), 5.78 (d, J=6.8Hz, 1H), 3.89-3.87 (m, 1H),2.06-1.92
(m,2H),1.75-1.60(m,3H),1.37-1.35(m,2H),1.24-1.09(m,3H).
13C NMR(100MHz,CDCl3)δ.167.6,163.0,138.3,133.5,133.0,131.8,130.2,128.7 (×2),128.4(×2),127.9,127.3,125.8,62.5,49.1,32.7(×2),25.5,24.8,24.7.
MS (+ESI): m/z (%)=415 (100) [M+H+].
(2) hydrolysis:
In 250mL round-bottomed flask, Ugi reaction product (7.8915g, 19.02mmol), anhydrous methanol are sequentially added (70mL), by 17.5mL H2The dense H of O and 17.5mL2SO4(98%) it is added dropwise in flask after mixing.It is heated in 90 DEG C of oil baths 2h is reacted, analyzes fully reacting through TLC.Extract after reaction solution in flask is adjusted to pH=7 with 5mol/L NaOH It takes, water is added and ethyl acetate washs 2 times, stratification, organic phase is dried, filtered with anhydrous sodium sulfate, rotates to obtain hydrolysis production Object, the dry 7.0243g that weighs to obtain, yield 96%.Reaction equation is as follows:
Product confirmation:
IR(film)3396,3349,2932,1674,1603,1508,747cm-1.
1H NMR(400MHz,CDCl3) δ 7.62 (d, J=8.8Hz, 1H), 7.49 (d, J=9.2Hz, 1H), 7.31 (d, J =8.4,7.6Hz, 1H), 7.21-7.14 (m, 3H), 6.75 (dd, J=7.2,7.2Hz, 1H), 6.57 (d, J=8.4Hz, 1H), 6.41 (br d, J=7.2Hz, 1H), 5.27 (s, 1H), 5.06 (br s, 1H), 5.09 (br s, 1H), 3.86-3.78 (m, 1H), 1.97 (d, J=15.2Hz, 1H), 1.77-1.70 (m, 2H), 1.60-1.58 (m, 2H), 1.45-1.12 (m, 5H), 1.08-1.02(m,1H).
13C NMR(100MHz,CDCl3)δ169.0,146.1,138.5,133.1,129.8,129.3,128.7(×2), 128.5,123.8,118.4,113.5(×2),61.2,48.4,32.8,32.5,25.4,24.5,24.4.
MS (+ESI): m/z (%)=386 (100) [M+].
(3) disperse dyes synthesize:
1, diazonium salt prepare: in 50mL round-bottomed flask be added 2,6- Dichloro-4-nitroaniline (0.8g, 3.885mmol, 1.5eq), by 4mLH2It is added drop-wise in flask after the dense HCl of O and 4mL (36.5%) mixing, it is under the conditions of 40 DEG C~60 DEG C that its is molten It solves (about 2h).After solution is cooled to room temperature, it is placed in ice-water bath.Sodium nitrite is used into (0.27g, 3.885mmol, 1.5eq) With 4mL H2O is dissolved in test tube, is placed in ice-water bath and is placed 2min or so, by above-mentioned NaNO2Aqueous solution is slowly added to dropwise, 2h is reacted in ice-water bath after being added dropwise to complete.
2, coupling reaction: in 100mL round-bottomed flask, being added 10mL methanol, 2mL acetic acid and 5mL water, in embodiment 2-1 (2) gained coupling component (1g, 2.59mmol, 1.0eq), stirring are completely dissolved to coupling component, under the conditions of ice-water bath, will make 2, the 6- Dichloro-4-nitroaniline diazonium salt got ready slowly instills dropwise, and thin-layer sample application tracks reaction process.It uses after completion of the reaction The NaOH of 5mol/L adjusts pH to alkalescent, filters, organic solvent (EA:PE=1:5) washing is obtained using re-crystallizing in ethyl acetate To dyestuff 2b, dry crude product 1.2713g, yield 81%.Reaction equation is as follows:
The IR of disperse dyes 2b,1H-NMR、13C-NMR and MS data are as follows:
IR(film)2927,1602,1515,1137,906,780cm-1.
1H NMR(400MHz,CDCl3) δ 8.26 (s, 2H), 7.83 (d, J=8.8Hz, 2H), 7.66 (dd, J=8.0, 1.2Hz, 1H), 7.49 (dd, J=7.6,1.6Hz, 1H), 7.34 (dd, J=6.8,6.8Hz, 1H), 7.23 (ddd, J=8.0, 8.0,2.0Hz, 1H), 6.60 (d, J=8.8Hz, 2H), 6.26 (d, J=4.8Hz, 1H), 6.08 (d, J=8.0Hz, 1H), 5.47 (d, J=4.8Hz, 1H), 3.83-3.75 (m, 1H), 1.99-1.95 (m, 1H), 1.72-1.69 (m, 2H), 1.62-1.56 (m,2H),1.43-1.19(m,4H),1.11-1.01(m,1H).13C NMR(100MHz,CDCl3)δ167.7,153.8, 150.2,145.3,144.8,137.6,133.2,130.2,128.9,128.3,127.9,126.4,124.2,123.1, 113.1,59.2,48.7,32.7,32.3,25.3,24.4,24.3.
MS (- ESI): m/z (%)=602 (75) [M-H+],604(100),606(39).
Embodiment 2-2:
Spectral absorption performance: weighing 0.05 gram of dyestuff 2b, dissolves constant volume in 50mL n,N-Dimethylformamide, dilution Certain multiple makes concentration 0.006g/L, is measured and is inhaled using UV-2450 ultraviolet-uisible spectrophotometer (Japanese Shimadzu Corporation) The curve of spectrum is received, and compared with 3 solution absorption spectra curve of same concentrations 0.006g/L disperse orange.See Fig. 3.
From the absorption spectrum curve in figure it can be found that compared with disperse orange 3, the maximum absorption wavelength of dyestuff 2b is to short Wave direction offsets by 51nm, becomes 416nm from original 467nm.After measured, specific performance index is as shown in following table 2-1:
Table 2-1, dyestuff absorption spectrum performance parameter
Dyestuff title Maximum absorption wavelength/nm Molar extinction coefficient ε
Disperse orange 3 467 30777
Dyestuff 2b 416 26158
Embodiment 2-3:
Product fastness properties detection: the dyeing by dyestuff 2b manufactured in the present embodiment and disperse orange 3, applied to terylene. Its test method is as follows, and dyeability result is as shown in table 2-2.
Test method: 0.5000g dyestuff 2b (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's Mother liquor draws this mother liquor into the dye liquor of various concentration, 180min is dyed under the conditions of 130 DEG C, obtains 1:1 standard color sample The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO105-P01:1993 (E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
Table 2-2, dyestuff compare the fastness properties of dyeing terylene
In terms of upper table experimental data: every fastness properties of dyestuff 2b and disperse orange 3 only have improvement slightly, still, Fastness to dryheat has achieved the effect that expected imagination, and staining fastness increase rate is larger, illustrates that dyestuff 2b really has fiber Biggish affinity, dyestuff are not easy to come out from internal migration.
Embodiment 2-4:
Dyeing by dyestuff 2b manufactured in the present embodiment and disperse orange 3, applied to Fypro.Its test method is such as Under, dyeability result is as shown in table 2-3.
Test method: 0.5000g dyestuff 2b (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's Mother liquor draws this mother liquor into the dye liquor of various concentration, 60min is dyed under the conditions of 100 DEG C, obtains 1:1 standard color sample The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO105-P01:1993 (E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
The fastness properties that table 2-3, dyestuff dye Fypro compare
In terms of upper table experimental data: dyestuff 2b has greatly improved than every fastness properties of disperse orange 3, to various fibres The staining fastness increase rate of dimension is larger, and especially fastness to dryheat has obtained large increase, illustrates dyestuff 2b really to fiber With very big affinity, dyestuff is not easy to come out from internal migration.

Claims (4)

1. a kind of disperse dye compound, structural formula are as shown in Equation 1:
In formula: R1For H, CH3, R2For H, Br.
2. a kind of disperse dye compound according to claim 1, which is characterized in that one kind selected from following compound:
。
3. a kind of synthetic method of disperse dye compound described in claim 1, which comprises the following steps: (1) Ugi reaction: in organic solvent, aldehyde, aniline, formic acid and cyclohexyl isonitrile are subjected to tetra- component reaction of Ugi, reaction solution passes through Filter, organic solvent washing obtain Ugi product；(2) hydrolysis: in alcohols solvent, Ugi product is added and acid carries out optional water Solution, reaction solution is neutralized, organic solvent is extracted, is concentrated under reduced pressure, is dried to obtain hydrolysate, that is, synthesizes the idol of azo dispersion dyes It is combined point；(3) coupling reaction: in the presence of organic acid, the in the mixed solvent of alcohols and water, by gained coupling component and 2,6- bis- Chloro-4 nitrophenyl diazonium salt, which is coupled, adjusts reacting liquid pH value, solid is filtered, washed, is dried etc. obtains shown in formula 1 Disperse dye compound.
4. a kind of purposes of the disperse dye compound described in claim 1 in polyester fiber and Fypro dyeing.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115637057A (en) * 2022-10-28 2023-01-24 绍兴文理学院 Synthesis method of double-crosslinking azo disperse dye

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Publication number Priority date Publication date Assignee Title
GB1328259A (en) * 1969-10-16 1973-08-30 Ciba Geigy Ag Intermediates for azo dyestuffs and process for their manu facture
US4026663A (en) * 1975-02-05 1977-05-31 American Color & Chemical Corporation Polyester fabric dyed with monoazo dyestuffs
WO2011084803A3 (en) * 2009-12-21 2011-11-24 Living Proof, Inc. Coloring agents and methods of use thereof
CN103079598A (en) * 2010-04-02 2013-05-01 药物影像股份有限公司 Single isomeric conjugates of rhodamine dyes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1328259A (en) * 1969-10-16 1973-08-30 Ciba Geigy Ag Intermediates for azo dyestuffs and process for their manu facture
US4026663A (en) * 1975-02-05 1977-05-31 American Color & Chemical Corporation Polyester fabric dyed with monoazo dyestuffs
WO2011084803A3 (en) * 2009-12-21 2011-11-24 Living Proof, Inc. Coloring agents and methods of use thereof
CN103079598A (en) * 2010-04-02 2013-05-01 药物影像股份有限公司 Single isomeric conjugates of rhodamine dyes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115637057A (en) * 2022-10-28 2023-01-24 绍兴文理学院 Synthesis method of double-crosslinking azo disperse dye
CN115637057B (en) * 2022-10-28 2023-10-20 绍兴文理学院 Synthesis method of double-crosslinking azo disperse dye

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